Pesticidal preparations comprising copolymers

ABSTRACT

The present invention relates to aqueous concentrates and solid formulations of pesticide preparations comprising copolymers which may be obtained by copolymerization of a) glycerol, b) at least one dicarboxylic acid, and c) at least one monocarboxylic acid of the formula (I)
 
R 1 —COOH   (I)
 
Where R 1  is (C 5 -C 29 )-alkyl; (C 7 -C 29 )-alkenyl; phenyl or naphthyl. The copolymer of the present invention increases the biological activity of the pesticide or herbicide.

This Application is a 35 U.S.C. 371 of PCT/EP2002/03827 filed on Apr. 6,2002 and claims benefit of German foreign application 101 17 993.6 filedon Apr. 10, 2001.

The invention relates to pesticide preparations comprising copolymersobtainable by copolymerization of glycerol, dicarboxylic acids andmonocarboxylic acids. The copolymers effect improved bioactivity of thepesticides (herbicides, insecticides, fungicides, bactericides,molluscicides, nematicides and rodenticides).

Crop protection agents are chemical or natural substances whichpenetrate plant cells, plant tissue or parasitic organisms in or on theplants and damage and/or destroy them. Herbicides make up the largestproportion of pesticides, followed by insecticides and fungicides.

The most important herbicides are chemical substances which act on thetransport system of plants, for example by inhibiting photosynthesis,fatty acid biosynthesis or amino acid biosynthesis, and which lead tothe inhibition of germination and growth or to the death of the plants.

The bioactivity of a pesticide can be determined by reference to plantgrowth or to the damage of the plants caused by the effect of the activeingredient on the leaf as a function of the activity time and the activeconcentration.

In order to develop the optimum pesticidal action, the pesticide mustwet the chlorophyll and remain there for a sufficiently long time, orpenetration of the active substance through the surface of the leaf mustbe achieved. A general problem here is that only a fraction of theactive substance developed the desired activity, i.e. is applied toharmful plants and grasses and can adhere thereto for a sufficientlylong time in order to penetrate the plant cells. By far the greatestpart is lost without developing its effect.

As described in a large number of patent specifications, in order toovercome this ecological and economic disadvantage, additives whichimprove the wettability, the solubility, the emulsifiability or theadsorption behavior of the active substance are added to the mostlyaqueous pesticide formulations. In addition, additives can facilitateand accelerate penetration of the active substances through the surfaceof the leaf into the plant.

WO 98/06259 describes a method of assisting bioactivity of cropprotection agents, according to which an aqueous surfactant solution issprayed onto the plants as coformulation together with or after theapplication of the active substance. The wetting agents used are aqueousorganosilicon and/or organofluorine compounds.

In EP 379 852 and U.S. Pat. No. 4,853,026 oils are added to theherbicide N-phosphonomethylglycine (glyphosate) as water-in-oilemulsions in order to improve the contact of the hydrophilic activeingredient with the lipophilic epidermis of the plants. A disadvantageis the inadequate stability of the emulsions.

According to WO 99/05914 an improvement in the action of anionicpesticides can be achieved by formulating the anionic active substancetogether with protonated polyamines or derivatives thereof as aqueouscolloidal dispersion.

U.S. Pat. No. 5,858,921 teaches that the concentration of glyphosate canbe reduced without reducing the bioactivity if water-soluble long-chainalkyldimethylamine oxides and water-soluble quaternary ammonium halidesare added to the formulation.

U.S. Pat. No. 5,750,468 describes glyphosate formulations which comprisetertiary or quaternary ether amines as adjuvant.

All of the hitherto described methods for improving the bioactivity ofpesticides are only successful to a limited extent. The object wastherefore to develop novel compositions or formulations of pesticides,in particular of herbicides of the N-phosphonomethylglycine (glyphosate)class of substance with improved effectiveness which are at the sametime cost-effective, easy to handle and well tolerated by humans and theenvironment. Glyphosate, being an environmentally very well toleratedand at the same time highly effective herbicide which can be usedwidely, is used in agriculture in large amounts. It is preferablyapplied as water-soluble salt, for example as alkali metal salt,ammonium salt, alkylamine salt, alkylsulfonium salt, alkylphosphoniumsalt, sulfonylamine salt or aminoguanidine salt or else as free acid inaqueous formulations, or else in solid form, with wetting agents toleaves and grasses, where it acts upon the transport system of theplants and destroys them.

Surprisingly, it has been found that the pesticidal action of cropprotection agents is significantly improved by the addition ofcopolymers obtainable by copolymerization of glycerol, dicarboxylicacid(s) and monocarboxylic acid(s).

The crosslinking of the polyglycerols by means of dicarboxylic acid(s)leads to network-like condensation products. Surprisingly, thecrosslinked polyglycerols exhibit a markedly higher effectiveness thanuncrosslinked polyglycerols.

The effectiveness can be influenced in a targeted manner via the degreeof crosslinking.

The crosslinking also advantageously effects increased electrolytestability of the agents. Moreover, the viscosity of the agents can beset via the degree of crosslinking.

The invention provides pesticide preparations comprising at least onecopolymer obtainable by copolymerization of

-   -   a) glycerol    -   b) at least one dicarboxylic acid and    -   c) at least one monocarboxylic acid according to formula (I)        R¹—COOH  (I),        where R¹ is (C₅-C₂₉)-alkyl; (C₇-C₂₉)-alkenyl; phenyl or        naphthyl.

The alkyl or alkenyl radicals R¹ may be linear or branched. The phenylor naphthyl radicals may be substituted, preferred substituents being(C₁-C₆)-alkyl, (C₁-C₆)-alkenyl, (C₁-C₆)-alkoxy, —CHO, —CO((C₁-C₆)-alkyl)or halogen.

Preferred dicarboxylic acids b) are oxalic acid; dicarboxylic acidsaccording to formula (II)HOOC—R²—COOH  (II)and/or dicarboxylic acids according to formula (III),

where

-   R² is a (C₁-C₄₀)-alkylene bridge, preferably (C₁-C₁₀)-alkylene,    particularly preferably (C₁-C₄)-alkylene, or a (C₂-C₂₀)-alkenylene    bridge, preferably (C₂-C₆)-alkenylene, particularly preferably    C₂-alkenylene, and-   R is one or more radicals chosen from H; (C₁-C₂₀)-alkyl, preferably    (C₁-C₆)-alkyl, particularly preferably (C₁-C₂)-alkyl;    (C₂-C₂₀)-alkenyl, preferably (C₂-C₆)-alkenyl; phenyl; benzyl;    halogen; —NO₂; (C₁-C₆)-alkoxy; —CHO or —CO((C₁-C₆)-alkyl). R² in    formula (II) may be linear or branched.

Formula (II) also includes dimerized fatty acids, such as, for example,the Pripol acids.

Particularly preferred dicarboxylic acids b) are oxalic acid, malonicacid, succinic acid, glutaric acid, adipic acid, pimelic acid, subericacid, fumaric acid, maleic acid, phthalic acid, isophthalic acid and/orterephthalic acid.

Particularly preferred dicarboxylic acids b) are phthalic acid,isophthalic acid and/or terephthalic acid.

A very particularly preferred dicarboxylic acid b) is phthalic acid.

Preferred monocarboxylic acids c) are those where R¹ is (C₇-C₂₂)-alkylor (C₇-C₂₂)-alkenyl.

Particularly preferred monocarboxylic acids c) are saturated orunsaturated fatty acids or mixtures thereof, such as, for example,coconut acid, oleic acid, lauric acid, tridecanoic acid, myristic acid,pentadecanoic acid, palmitic acid, margaric acid, stearic acid,nonadecanoic acid, arachidic acid, behenic acid, linoleic acid,linolenic acid, palmitic acid and tallow fatty acid.

Particularly preferred monocarboxylic acids c) are coconut acid andtallow fatty acid.

A very particularly preferred monocarboxylic acid c) is coconut acid.

Particularly advantageous copolymers are those obtainable bycopolymerization of glycerol, phthalic acid and coconut acid.

Preferably, the copolymers comprise 19.9 to 99% by weight of structuralunits originating from component a), 0.1 to 30% by weight of structuralunits originating from component b) and 0.9 to 80% by weight ofstructural units originating from component c).

The copolymers particularly preferably comprise 50 to 90% by weight ofstructural units originating from component a), 1 to 25% by weight ofstructural units originating from component b) and 2 to 49% by weight ofstructural units originating from component c).

A content of from 1 to 10% by weight of structural units originatingfrom component b) is particularly advantageous for the properties of thecopolymers.

The copolymers advantageously have an OH number of from 400 to 1000 mgof KOH/g (determination in accordance with DIN 53240).

The viscosity of the 100% pure copolymers, measured at 60° C. using arotary viscometer, is advantageously in the range from 1500 mPas to35000 mPas. Higher viscosities are possible, but hinder handling of thesubstances. The copolymers are advantageously handled as 75 to 90%strength by weight aqueous solution.

The copolymers are obtainable by copolymerization of

-   -   a) glycerol    -   b) at least one dicarboxylic acid and    -   c) at least one monocarboxylic acid according to formula (1).

The copolymerization is preferably carried out by firstly polymerizingthe glycerol component a) to give polyglycerol and then copolymerizingthe polyglycerol and a mixture of dicarboxylic acid component b) andmonocarboxylic acid component c).

In another preferred variant, the glycerol component a) is firstlypolymerized to give polyglycerol, then the dicarboxylic acid componentb) is copolymerized and then the monocarboxylic acid component c) iscopolymerized.

In a likewise preferred variant, the glycerol component a) is firstlypolymerized to give polyglycerol, then the monocarboxylic acid componentc) is copolymerized and then the dicarboxylic acid component b) iscopolymerized.

However, the copolymerization is not limited to the above variants.

For example, variants in which some of the glycerol a) is polymerized tooligomers and then the dicarboxylic acid component b), themonocarboxylic acid component c) and the remaining glycerol a)copolymerized may also be advantageous.

Advantageous embodiments of the copolymerization are described by way ofexample below.

A) Polymerization of the Glycerol to Oligoglycerols or Polyglycerol:

The polymerization of the glycerol to oligoglycerols or polyglycerolscan take place as standard in a stirred apparatus with water separatorat 240 to 270° C. and with nitrogen introduction. The catalyst used is50% strength sodium hydroxide solution in a concentration range from 0.1to 0.4% by weight. After 5 to 20 hours, depending on the desired degreeof polymerization, the polymerization is ended. A sample is taken andthe OH number is determined. The average molar mass of theoligoglycerols or polyglycerols can be calculated from the OH number.

B) One-Pot Process with Prepolymerized Polyglycerol:

The polyglycerol is mixed in the molten state in a stirred containerwith water separator with the dicarboxylic acid and the monocarboxylicacid in the desired molar ratio and heated, with stirring, for 7 hoursat 200-240° C. The acid number of the finished product is less than 1 mgof KOH/g.

C) Polyglycerol is Firstly Copolymerized (Crosslinked) with theDicarboxylic Acid and then Copolymerized with the Monocarboxylic Acid:

The polyglycerol is mixed in the molten state in a stirred containerwith water separator with the dicarboxylic acid in the desired molarratio and heated, with stirring, for 2 hours at 200-240° C. Theresulting product is clear and homogenous. The monocarboxylic acid isthen added and esterified for 5 hours at 200-240° C. The acid number ofthe end-product is less than 1 mg of KOH/g.

D) Polyglycerol is Firstly Copolymerized with the Monocarboxylic Acidand then Copolymerized (Crosslinked) with the Dicarboxylic Acid:

The polyglycerol is mixed in the molten state in a stirred containerwith water separator with the monocarboxylic acid in the desired molarratio and heated, with stirring, for 5 hours at 200 to 240° C. Theresulting product has an acid number <1 mg of KOH/g. The dicarboxylicacid is then added in the desired molar ratio and esterified for 2 hoursat 200 to 240° C. The acid number of the end-product is less than 1 mgof KOH/g.

The copolymers are suitable as adjuvants in pesticide formulation forimproving the bioactivity of herbicides, insecticides, fungicides,acaricides, bactericides, molluscicides, nematicides and rodenticides.

The copolymers are preferably used in herbicide formulations.

Particularly suitable herbicides are glyphosate(N-phosphonomethylglycine) and salts and/or derivatives thereof.Examples of suitable water-soluble salts are the alkali metal salts,ammonium salts, alkylamine salts, alkylsulfonium salts, alkylphosphonium[lacuna], sulfonylamine salts or aminoguanidine salts. Examples offurther suitable herbicides are acifluorfen, asulam, benazolin,bentazone, bilanafos, bromacil, bromoxynil, chloramben, clopyralid,2,4-D, 2,4-DB, dalapon, dicamba, dichlorprop, diclofop, endothall,fenac, fenoxaprop, flamprop, fluazifop, flumiclorac, fluoroglycofen,fomesafen, fosamine, glufosinate, haloxyfop, imazapic, imazamethabenz,imazamox, imazapyr, imazaquin, imazethapyr, loxynil, MCPA, MCPB,mecoprop, methylarsenic acid/MSMA, naptalam, picloram, quinclorac,quizalofop, 2,3,6-TBA and TCA.

The pesticide preparations according to the invention can comprise thecopolymers in virtually any concentration.

Particularly preferred formulations are “tank-mix” and “ready to usecompositions” which comprise 0.001 to 10% by weight, preferably 0.05 to2% by weight, of pesticide and 0.01% by weight to 10% by weight,preferably 0.1% by weight to 2% by weight, particularly preferably 0.2%by weight to 1% by weight, of copolymers. The weight ratio of copolymersto pesticide is here preferably between 1:10 and 500:1, particularlypreferably 1:4 and 4:1.

Concentrate formulations which are diluted prior to use can comprise thepesticide in amounts of from 5 to 60% by weight, preferably 20 to 40% byweight, and the copolymers in amounts of from 3 to 50% by weight. Theweight ratio of copolymers to pesticides is here preferably between 1:20and 1:1, preferably 1:10 and 1:2.

Alternatively, the formulations according to the invention can beprepared in solid form as powders, pellets, tablets or granulates, whichare dissolved in water prior to use. Solid preparations can comprise thepesticide in amounts of from 20 to 80% by weight, preferably 50 to 75%by weight, particularly preferably 60 to 70% by weight and thecopolymers in amounts of from 5 to 50% by weight, preferably 10 to 30%by weight.

The pesticide preparations can, moreover, comprise the customarythickeners, antigelling agents, anti-freeze agents, solvents,dispersants, emulsifiers, preservatives, further adjuvants, binders,antifoams, thinners, disintegrants and wetting agents.

Thickeners which may be used are xanthan gum and/or cellulose, forexample carboxy-, methyl-, ethyl- or propylcellulose. The finishedcompositions preferably comprise 0.01 to 5% by weight of thickeners.

Suitable solvents are monopropylene glycol, animal and mineral oils.

Suitable dispersants and emulsifiers are nonionic, amphoteric, cationicand anionic surfactants.

Preservatives which may be used are organic acids and their esters, forexample ascorbic acid, ascorbyl palmitate, sorbate, benzoic acid, methyland propyl 4-hydroxybenzoate, propionates, phenol, for example 2-phenylphenate, 1,2-benzisothiazolin-3-one, formaldehyde, sulfurous acid andsalts thereof.

Suitable antifoams are polysilicones.

Other adjuvants which may be used are alcohol ethoxylates, alkylpolysaccharides, fatty amine ethoxylates, sorbitan and sorbitolethoxylate derivatives and derivatives of alk(en)ylsuccinic anhydride.

The mixing ratio of these adjuvants to the copolymers is preferably inthe range 1:10 to 10:1.

Suitable binders for solid formulations are polyvinylpyrrolidone,polyvinyl alcohol, carboxymethylcellulose, sugars, for example sucrose,sorbitol, or starch.

Suitable thinners, absorbers or carriers are carbon black, tallow,kaolin, aluminum stearate, calcium stearate or magnesium stearate,sodium tripolyphosphate, sodium tetraborate, sodium sulfate, silicatesand sodium benzoate.

Suitable disintegrants are cellulose, for examplecarboxymethylcellulose, polyvinylpyrrolidone, sodium acetate orpotassium acetate, carbonates, bicarbonates, sesquicarbonates, ammoniumsulfate or potassium hydrogenphosphate.

Wetting agents which may be used are alcohol ethoxylates/propoxylates.

The pesticide preparations preferably have a pH of from 4 to 8,particularly preferably 6 to 7.

The formulations according to the invention can be used in accordancewith customary methods.

Aqueous concentrates and solid formulations are diluted with thecorresponding amount of water prior to application. Preferably, 0.1 to 5kg, preferably 0.3 to 2.5 kg, of pesticide are applied per hectare. Theproportion of the copolymers is preferably 0.1 to 3.0 kg/ha. The amountof pesticide preparation for spray application is preferably 50 to 1000l/ha.

The properties of the copolymers or pesticide preparations, such as, forexample, solubility in water, electrolyte stability, viscosity andcompatibility with crop protection agent active ingredients canadvantageously be very readily set via the degree of crosslinking. Forthe degree of crosslinking, the nature and content of the dicarboxylicacid component b) are decisive, the content being of particularimportance.

Surprisingly, it has been found that high-concentration aqueousformulations of anionic pesticides, in particular glyphosate in saltform, and copolymers are phase stable. Even in cases of prolongedstorage period, no crystallization of the ionic components is observed.

In addition to the high electrolyte stability, the use of the copolymersaccording to the invention effects an improvement in the compatibilityand the contactability of the hydrophilic active ingredient with thelipophilic epidermis of the plants.

A good wettability and absorption capacity of the pesticide formulationsaccording to the invention aids the bioactivity in the active ingredientin the plants.

The invention also provides a method of increasing the bioactivity ofpesticides, which involves using the pesticides in the form of pesticidepreparations comprising copolymers obtainable by copolymerization of

-   -   a) glycerol    -   b) at least one dicarboxylic acid and    -   c) at least one monocarboxylic acid according to formula (I).

The method is preferably suitable for herbicides, in particular forglyphosate, and salts and/or derivatives thereof.

EXAMPLES

The examples below demonstrate the influence of the copolymers on thebioactivity of the herbicide glyphosate.

1) Preparation of the Copolymers I to V

Preparation of Polyglycerol where n=9.7:

2000 g of glycerol and 6.0 g of NaOH (50%) were heated to 270° C. in astirred apparatus with nitrogen introduction and water separator withstirring. After a reaction time of 9 hours and a discharge of 444 g ofwater, a sample was taken and the OH number was determined. The OHnumber determined was 891 mg of KOH/g. This corresponds to an averagedegree of condensation n of 9.7 glycerol units. The degree ofcondensation can also be determined approximately via the viscosity orthe refractive index of the reaction mixture. For this purpose, it isnecessary to construct a calibration curve beforehand.

Preparation of Copolymer I:

180.00 g of polyglycerol n=9.7 (0.243 mol) were added to a stirredcontainer with N₂ introduction and water separator and treated with24.70 g of coconut fatty acid (C₈/₁₈) (0.121 mol) and 10.13 g ofphthalic acid (0.061 mol). The reaction mixture was then heated, withstirring, at 220° C. for 7 hours. The copolymer had an acid number of0.40 mg of KOH/g.

Preparation of Copolymer II:

190.00 g of polyglycerol where n=9.7 (0.256 mol) were introduced into astirred container with N₂ introduction and water separator and treatedwith 26.11 g of coconut fatty acid (C₈/₁₈) (0.128 mol) and 4.32 g ofphthalic acid (0.026 mol). The reaction mixture was then heated at 220°C. for 7 hours with stirring. The copolymer had an acid number of 0.46mg of KOH/g.

Preparation of Copolymer III:

185.00 g of polyglycerol where n=9.7 (0.256 mol) were introduced into astirred container with N₂ introduction and water separator and treatedwith 4.25 g of phthalic acid (0.0256 mol) for two hours at 215° C. Thereaction mixture was clear and homogenous. 25.50 g of coconut fatty acid(C₈/₁₈) (0.125 mol) were then introduced into the stirred container andreacted for 5 hours at 215° C. The copolymer had an acid number of 0.38mg of KOH/g.

Copolymer IV:

185.00 g of polyglycerol where n=9.7 (0.256 mol) were introduced into astirred container with N₂ introduction and water separator andcrosslinked with 10.38 g of phthalic acid (0.0625 mol) for two hours at215° C. The reaction mixture was clear and homogeneous. 25.50 g ofcoconut fatty acid (C₈/₁₈) (0.125 mol) were introduced into the stirredcontainer and reacted for 5 hours at 215° C. The copolymer had an acidnumber of 0.53 mg of KOH/g.

Copolymer V:

180.00 g of polyglycerol where n=9.7 (0.243 mol) were introduced into astirred container with N₂ introduction and water separator andesterified with 24.75 g of coconut fatty acid (C₈/C₁₈) (0.121 mol), anacid number of 0.14 mg of KOH/g being achieved after 5 hours and anesterification temperature of 215° C. 4.03 g of phthalic acid were thenadded and crosslinked for 2 hours at 215° C. The reaction end-productwas clear and homogenous.

Preparation of test formulations comprising the copolymers I to V

Test formulations were prepared with in each case 200 g, 300 g and 500 gof glyphosate and in each case 600 g of the copolymers I to V in 300 lof water. The data by weight refer to 100% active ingredient and 100%adjuvant. An amount of the formulation corresponding to the ratio 300l/ha was applied in a greenhouse to the plant species Abutilontheophrasti (ABUTH), Sesbania exaltata (SEBEX), Pharbitis purpurea(PHBPU), Galium aparine (GALAP), Amaranthus retroflexus (AMARE) andEchinochloa crus-galli (ECHCG), and, after 21 days at 20° C., the plantgrowth was assessed according to a % scale.

0% means no effect and 100% means complete destruction of the types ofplant. The effect of the copolymers I to V on the herbicidal action ofglyphosate is shown in Table 1.

TABLE 1 Effect of the copolymers I-V on the herbicidal action ofglyphosate Glyphosate Copoly- (g/ha) mers SEBEX AMARE GALAP ABUTH ECHCGPHBPU Total 200 — 10 20 5 0 15 10 10 300 — 15 45 20 10 20 20 22 500 — 3065 40 15 40 40 38 200 I 75 80 25 20 70 45 53 300 I 85 85 50 55 85 65 70500 I 95 90 75 75 90 85 85 200 II 35 70 45 25 65 30 45 300 II 50 85 7050 80 55 65 500 II 90 95 80 70 95 80 85 200 III 40 65 35 20 60 20 40 300III 65 80 60 50 70 35 60 500 III 85 85 70 65 85 55 74 200 IV 45 70 55 3045 30 46 300 IV 65 85 65 50 65 50 63 500 IV 95 90 70 65 90 80 82 200 V35 70 25 15 50 35 38 300 V 50 85 45 40 75 65 60 500 V 60 95 70 65 90 9579

It is clear that the copolymers effected a significant increase in theherbicidal action of glyphosate.

1. A pesticide preparation comprising at least one pesticide and atleast one copolymer obtained by copolymerization of a) glycerol, b) atleast one dicarboxylic acid, and c) at least one monocarboxylic acid ofthe formula (I)R¹—COOH  (I) where R¹ is (C₅-C₂₉)-alkyl; (C₇-C₂₉)-alkenyl; phenyl ornaphthyl, wherein the copolymers comprise 19.9 to 99% by weight ofcomponent a), 0.1 to 30% by weight of component b) and 0.9 to 80% byweight of component c).
 2. The pesticide preparation as claimed in claim1, wherein the dicarboxylic acid b) is oxalic acid; a dicarboxylic acidaccording to formula (II)HOOC—R²—COOH  (II) and/or a dicarboxylic acid according to formula (III)

wherein R² is a (C₁-C₄₀)-alkylene bridge or a (C₂-C₂₀)-alkenylene bridgeand R is one or more radicals selected from the group consisting of H,(C₁-C₂₀)-alkyl, (C₂-C₂₀)-alkenyl, phenyl, benzyl, halogen, —NO₂,(C₁-C₆)-alkoxy, —CHO, —CO((C₁-C₆)-alkyl), and mixtures thereof.
 3. Thepesticide preparation as claimed in claim 1, wherein the dicarboxylicacid b) is selected from the group consisting of oxalic acid, malonicacid, succinic acid, glutaric acid, adipic acid, pimelic acid, subericacid, fumaric acid, malic acid, phthalic acid, isophthalic acid,terephthalic acid, and mixtures thereof.
 4. The pesticide preparation asclaimed in claim 1, wherein the dicarboxylic acid b) is selected fromthe group consisting of phthalic acid, isophthalic acid, terephthalicacid, and mixtures thereof.
 5. The pesticide preparation of claim 1,wherein the monocarboxylic acid c) is a fatty acid or a mixture of fattyacids.
 6. The pesticide preparation of claim 1, wherein themonocarboxylic acid c) is selected from the group consisting of coconutacid, tallow fatty acid, and mixtures thereof.
 7. The pesticidepreparation of claim 1, wherein the dicarboxylic acid b) is phthalicacid and the monocarboxylic acid c) is coconut fatty acid.
 8. Thepesticide preparation of claim 1, wherein the copolymer comprises 1 to10% by weight of component b).
 9. The pesticide preparation of claim 1,wherein the copolymers have an OH number of from 400 to 1000 mg ofKOH/g.
 10. The pesticide preparation of claim 1, wherein the copolymercomprises a viscosity at 60° C. in the range of 1500 mPas to 35000 mPas.11. The pesticide preparation of claim 1, wherein during thecopolymerization, firstly the glycerol component a) is polymerized to apolyglycerol, and then the polyglycerol and a mixture of thedicarboxylic acid component b) and the monocarboxylic acid component c)are copolymerized.
 12. The pesticide preparation of claim 1, wherein theglycerol component a) is firstly polymerized to polyglycerol, then thedicarboxylic acid component b) is copolymerized and then themonocarboxylic acid component c) is copolymerized.
 13. The pesticidepreparation of claim 1, wherein the glycerol component a) is firstlypolymerized to polyglycerol, then the monocarboxylic acid component c)is copolymerized and then the dicarboxylic acid component b) iscopolymerized.
 14. The pesticide preparation of claim 1, wherein thepesticide is selected from the group consisting of herbicides,insecticides, fungicides, bactericides, molluscicdes, nematicides,rodenticides, and mixtures thereof.
 15. The pesticide preparation ofclaim 1, wherein the pesticide is an herbicide.
 16. The pesticidepreparation of claim 15, wherein the herbicide is selected from thegroup consisting of glyphosate, glyphosate salts, and mixtures thereof.17. The pesticide preparation of claim 1, which is in a form selectedfrom the group consisting of a “tank-mix”, “ready to use composition”,concentrate, powder, pellet, tablet, and granulate.
 18. A method forincreasing the bioactivity of at least one pesticide, said methodcomprising adding to the pesticide at least one copolymer obtained bycopolymerization of a) glycerol, b) at least one dicarboxylic acid, andc) at least one monocarboxylic acid of the formula (I)R¹—COOH  (I) where R¹ is (C₅-C₂₉)-alkyl: (C₇-C₂₉)-alkenyl; phenyl ornaphthyl, wherein the copolymers comprise 19.9 to 99% by weight ofcomponent a), 0.1 to 30% by weight of component b) and 0.9 to 80% byweight of component c).
 19. The pesticide preparation as claimed inclaim 1, wherein the dicarboxylic acid b) is phthalic acid.
 20. Thepesticide preparation of claim 1, wherein the monocarboxylic acid c) iscoconut acid.
 21. The pesticide preparation as claimed in claim 1,wherein the pesticide preparation is in the form of a concentrateformulation having from 5 to 60% by weight of the pesticide and from 3to 50% by weight of the copolymer.
 22. The pesticide preparation ofclaim 21 wherein the concentrate formulation has a weight ratio ofcopolymer to pesticide of from 1:20 to 1:1.
 23. The pesticidepreparation of claim 21 wherein the concentrate formulation is a phasestable aqueous concentrate.